JPH06172670A - Reactive dye, its preparation and its use - Google Patents

Abstract

PURPOSE: To obtain a new reactive dyestuff useful for dyeing cellulose fibers, or the like, excellent in reactivity and build-up property and giving a cardinal, orange or yellow dyed body.

CONSTITUTION: This reactive dyestuff of formula I [where D is the radical of an org. dyestuff of monoazo, polyazo or metallic complex azo series; W is a direct bond or a crosslinking member; R¹ is H, OR, OSO₃H, SO₃H, COOR or the like (R is H, CH₃ or C₂H₅); R² is H, a 1-4C alkyl, Cl, Br, COOH or the like; (i) is 0 or 1; (j) is 0-2; (r) is 2 or 3; X is F, Cl or Br; Z is -CH=CH₂, -CH₂-CH₂-OSO₃H, -CH₂-CH₂-Cl or the like; and (n) is 1 or 2], excluding compds. of formulae II-IV, e.g. a compd. of formula V is obtd. by condensing a compd. of formula VI with n-mol compd. of formula VII.

COPYRIGHT: (C)1994,JPO

Description

Detailed Description of the Invention

The present invention relates to novel di- and polyfunctional reactive dyes,
Regarding its manufacture and use.

Bifunctional reactive dyes are, for example, DE-A-
2 614 550, EP-A-70 807, EP-
Known from A-70 806 and EP-A-74 928, tri- and tetra-functional reactive dyes are, for example, EP-A.
No. 3,395,951, the known reactive dyes still have various drawbacks in their application, eg too low fixation yields.

The present invention is a formula

[0004]

[Chemical 12]

[Wherein D represents a group of an organic dye of a monoazo, polyazo or metal complex azo type, W represents a direct bond or a bridging member, R ¹ is H, OR, OSO
₃ H, SO ₃ H, COOR or C ₁ -C ₄ -alkyl optionally substituted by halogen, R being H,
CH ₃ or indicates C ^₂ H _5, R ₂ is H, C ₁ -C ₄ - _{alkyl, Cl, Br, C 1 -C} 4 - an alkoxy or COOH, i denotes 0 or 1, j is 0 1 or 2
r represents 2 or 3, preferably 2, X represents F, Cl or Br, and Z represents —CH═CH ₂ , —CH ₂ —CH ₂ —O.
_{SO 3 H, -CH 2 -CH 2} -Cl, -CH 2 -CH 2 -B
_{r, -CH 2 -CH 2 -S 2} O 3 H, -CH 2 -CH 2 -O-
_{CO-CH 3, -CH 2 -CH} 2 -OPO 3 H 2 or -CH ₂
--CH ₂ --OH, n represents 1 or 2], and a compound known from EP-A-70 806

[0006]

[Chemical 13]

[0007]

[Chemical 14]

The present invention relates to a novel reactive dye excluding.

Particularly preferred groups Z are --CHCH ₂ and --C ₂ H ₄ --OSO ₃ H.

The following are alkyl, aryl, aralkyl, hetaryl, alkoxy, as mentioned in this application:
Applies to halogen and acylamino groups, and bridging members: Alkyl groups especially have 1 to 4 carbon atoms, optionally halogen, such as Cl or Br, OH, C
It is understood to mean those which may contain substituents such as N, CO ₂ H, SO ₃ H or OSO ₃ H.

Alkoxy groups are understood to mean in particular those having 1 to 4 carbon atoms.

Halogen is understood to mean in particular chlorine or fluorine.

Acylamino radicals are understood to mean in particular those having 1 to 4 carbon atoms, for example formylamino, acetylamino, propionylamino or n-butyrylamino.

Suitable bridging members W include, for example:

[0015]

[Chemical 15]

[0016] O ₂ —, wherein R _w represents halogen or alkyl, alkylene represents an alkylene group having 1 to 6 carbon atoms, and * represents an atom or group bonded to the chromophore D.

The alkylene groups which may be mentioned are: - (CH _{3) 4} - or - (CH _{2) 6} - is.

The invention further relates to the preparation of the reactive dyestuffs of the formula (I) by a method known per se, which process comprises the steps of a)

[0019]

[Chemical 16]

[Wherein D, E, R ¹ and n are as defined above] and n mol

[0021]

[Chemical 17]

By condensation of the trihalogenotriazine of the formula

[0023]

[Chemical 18]

A compound of formula (IV) is obtained by

[0025]

[Chemical 19]

Further condensation with a component of the formula wherein R ² , i, j, r, X and Z are as defined above, or b) in the reverse order, the trihalogenotriazine of formula (III) A first condensation product of the condensation of the component of formula (V) with

[0027]

[Chemical 20]

[Wherein X, i, R ² , j, r and Z have the same meanings as defined above] to further condense n moles of the compound of formula (VI) with the dye of formula (II). Or c) condensation of a suitable starting material with trihalogenotriazine (III) and components of formula (V), or suitable starting material with formula (V)
By condensation of the first condensation product of I) and subsequent dye synthesis.

The present invention further provides a compound of formula (V), and an intermediate of formula (V)

[0030]

[Chemical 21]

[Wherein R ² , Z, j, i and r have the same meanings as in formula (I)], including a salt and a reaction product with a protecting group, and described in Bul. Inst. Polite
h. Iasi 16 (1970) 213-220 (CA
75: 119130f). Feldman
and I. By Negulescu and RO
59 096 of 15th Novemer 1
973 (CA 81: 50515q). Ne
compounds described as monomers of acrylonitrile / vinyl sulfone copolymers by Gulescu

[0032]

[Chemical formula 22]

With the exception of

Particularly preferred compounds are those in which R ² represents H,
It is a compound in which j and i are 0 and r is 2.

The compound of formula (V) has the formula

[0036]

[Chemical formula 23]

By sulfation of the compound of and subsequent reaction with mercaptoethanol

[0038]

[Chemical formula 24]

By optionally protecting the NH group with a protecting group, in particular acetyl, and in particular oxidizing with H ₂ O _2.

[0040]

[Chemical 25]

And optionally cleaving the protecting group

[0042]

[Chemical formula 26]

And optionally converting the group SO ₂ C ₂ H ₄ —OH to the vinylsulfonyl group or the —CH ₂ —CH ₂ —OH group to the other removable groups mentioned as Z. It can be manufactured by conversion.

The condensation of the starting components with the trihalogenotriazine can be carried out in any order, in an aqueous or organic aqueous medium by acid-condensation.
Performed in the presence of a binder. Depending on the nature of the starting components, the first stage of condensation in this case is pH 2-8, preferably 3-7.
And at a temperature of 0-40 ° C, preferably 0-25 ° C. The substitution of the second halogen atom of triazine is pH
In the range 4-10, preferably 5-9, and 0-60
C., preferably 0-30.degree. C.

Acid-binding agents are, for example, carbonates, hydroxides or phosphates such as sodium carbonate, sodium bicarbonate,
Dilute sodium hydroxide solution, disodium or trisodium phosphate or sodium fluoride.

If the dye solution or liquid dye composition is directly obtained by condensation or dye synthesis, it is advantageous to use lithium carbonate or lithium hydroxide, optionally with a solubilizer and / or a stabilizing buffer system. Other conversion reactions of the dye or its precursors, such as metallation reactions, sulfonations or introduction of acylamino groups can generally be carried out at any desired stage of dye synthesis.

Particularly useful dyes in this system are water-soluble azo dyes, especially those containing sulfonic acid and / or carboxylic acid groups. Dyes can be metal-free or metal-containing, of the copper complexes, the copper, nickel, chromium and cobalt complexes are preferred and of interest.

The dyes which comprise suitable dye groups D or amino groups and which are the basis of the dyes of the formula (I) are described in large numbers in the literature. Examples of this are: E
P-A 54 515, EP-A 69 703, EP
-A 70 807, EP-A 497 174, DE
-A 3 222 726, DE-A 2 650 5
55, DE-A 3 023 855, DE-A 2
847 938, DE-A 2 817 780, GB
-A2 057 479, DE-A2 916 71
5, DE-A 2 814 206, DE-A 3 0
1993, EP-A 45 488 and Venkat.
araman: The Chemistry of S
synthetic Dyes, volume VI, c
chapter II, page 211-325, Ne
w York, London; 1972.

Preferred groups of organic dyes are, for example:

[0050]

[Chemical 27]

Corresponding to, Di is a benzene or naphthalene system optionally substituted by substituents customary in azo chemistry, for example hydroxyl, methyl, ethyl, methoxy or ethoxy groups, optionally substituted having 2 carbon atoms.
-4 is an alkanoylamino group, an optionally substituted benzoylamino group of the diazo component or a halogen atom and SO ₂ -Z, K is optionally a substituent customary in azo chemistry, such as hydroxyl, amino, methyl. , A benzene, naphthalene or ketomethylene system substituted with an ethyl, methoxy or ethoxy group, an optionally substituted alkanoylamino group having 2 to 4 carbon atoms, a group of a coupling component of an optionally substituted benzoylamino group or a halogen A represents an atom, M is a benzene or naphthalene system optionally substituted by a substituent usually used in azo chemistry, for example, a hydroxyl, methyl, ethyl, methoxy or ethoxy group, an optionally substituted alkanoyl having 2-4 carbon atoms. Amino group, optionally substituted benzoyl Roh represents a group or a halogen atom of the central components of the group, Di, M and K together at least two sulfonic acid groups, preferably containing 3-4 sulfonic acid groups.

Important azo dyes are, for example, benzene-azo-
Naphthalene type, bis- (benzene-azo) -naphthalene type, benzene-azo-5-pyrazolone type, benzene-azo-benzene type, naphthalene-azo-benzene type, benzene-azo-aminonaphthalene type, naphthalene-azo-
Naphthalene type, naphthalene-azo-5-pyrazolone type,
Benzene-azo-pyridone type dyes, benzene-azo-aminopyridine type dyes, naphthalene-azo-pyridone type dyes, naphthalene-azo-aminopyridine type dyes and stilbene-azo-benzene type dyes, and dyes containing sulfonic acid groups are also used in this case. preferable. In the case of a metal complex azo dye, the group bonded as a metal complex is preferably in the o-position with respect to the azo group, for example, o, o'-dihydroxy-, o-hydroxy-o'-carboxy-, o-carboxy. It is preferably in the form of -o'-amino- and o-hydroxy-o'-amino-azo groups.

Preferred reactive dyes are of the formula

[0054]

[Chemical 28]

[Wherein D is a group of an organic dye of a monoazo, polyazo or metal complex azo type, and further does not contain a fiber-reactive group, and R ¹ and R ² are independently of each other H, CH ₃
Or C ₂ H ₅ and W is a direct bond or a bridging member,
Preferably an alkylene or a direct bond, i is 0 or 1, j is 0 or 1, X is F or Cl, Z is CH ₂ -CH ₂ -OSO ₃ H or CH = CH ₂ And n is 1 or 2].

Particularly preferred reactive dyes are of the formula

[0057]

[Chemical 29]

[Wherein D is a group of an organic dye of a monoazo, polyazo or metal complex azo type, does not further contain a fiber-reactive group, X is F, Z is CH ₂ —CH ₂ — OS
O ₃ H, R ¹ is H, and n is 1.].

Preferred dyes are represented by the following formulas (1)-(42)
Is a dye of the formula

[0060]

[Chemical 30]

Containing groups X, i, R ² , j, r and Z
Is synonymous with formula (I):

[0062]

[Chemical 31]

Here, Sa = OCH ₃ or OC ₂ H ₅

[0064]

[Chemical 32]

[0065]

[Chemical 33]

[0066]

[Chemical 34]

Metal complexes of the dyes of the formulas (12)-(42):

[0068]

[Chemical 35]

[0069]

[Chemical 36]

Cu (1: 1 complex) or Cr and Co
(1: 2 complex) is preferable as the metal atom. Cr and C
The o-complex can contain one or two molecules of the azo compound of the above formula, ie they can be symmetrically or asymmetrically constructed with other desired ligand groups.

[0071]

[Chemical 37]

[0072]

[Chemical 38]

[0073]

[Chemical Formula 39]

[0074]

[Chemical 40]

[0075]

[Chemical 41]

[0076]

[Chemical 42]

[0077]

[Chemical 43]

Wherein acyl is, for example, acetyl or optionally substituted benzoyl, R ¹⁴ ═H or C ₁ -C ₂ — optionally substituted by SO ₃ H or NH _2.
Alkyl, R ¹ = H, CH ₃ or C ₂ H ₅ , R ³ = H or sulfo, R ⁵ = H, CH ₃ , OCH ₃ or Cl, R ⁶ = H, C
₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, Cl, B
r, COOH or SO ₃ H, R ⁷ = H, OH, NH ₂ , N
_{HCOCH 3, NHCOPh, Cl, C} 1 -C 4 - alkoxy or C ₁ -C ₄ - _{^{alkyl, R 8 = H, SO 3}} H, CH
₂ SO ₃ H, Cl, C ₁ -C ₄ -alkylsulfonyl, C
N, carbon amide, especially CONH ₂ , R ⁹ = H, C ₁ -C ₄
- alkyl, C ₁ -C ₄ - alkoxy, Cl, Br, acylamino in particular C ₁ -C ₄ - alkylcarbonylamino or arylcarbonylamino, phenyl carbonylamino optionally substituted e.g., C ₁ -C ₄ - alkylsulfonylamino , Aminocarbonylamino, C ₁ -C ₄ -alkylsulfonylamino or arylsulfonylamino, and R ¹⁰ = H, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, OH or SO ₃ H.

The fused ring indicated by the dashed line indicates that a naphthalene system is alternatively possible.

Particularly preferred reactive dyes are those of the formula (I): X = Cl, i = 0, j = 0 or 1, Z = -CH _{2
-CH 2 -OSO 3 H, -CH =} CH 2 or -CH ₂ -CH
₂ -Cl, and a reactive dye of R ² = H.

Particularly preferred reactive dyes are also those of the formula (I) in which X = F, i = 0, j = 0, Z = -CH.
₂ -CH ₂ -OSO ₃ H or -CH = CH _2, and R ² = H
Reactive dye of formula (I) and Z = -CH ₂ -C
It is a reactive dye of H ₂ -SO ₃ H.

In formula (I) a group D, preferably a group of organic dyes from the monoazo or polyazo system, is substituted by one or two groups Z'-O ₂ S- (CH ₂ ) _0-1. Where Z ′ is —CH═CH ₂ ,
_{-CH 2 -CH 2 -OSO 3 H,} -CH 2 -CH 2 -Cl,
_{-CH 2 -CH 2 -Br, -CH 2} -CH 2 -S 2 O 3 H, -
_{CH 2 -CH 2 -O-CO-} CH 3, -CH 2 -CH 2 -O
PO ₃ reactive dyes is H ₂ or -CH ₂ -CH ₂ OH is preferred.

Particularly preferred reactive dyes are those of the formula (I) in which the radical D, preferably the radical of the organic dye from the monoazo or polyazo system, has 1 or 2 radicals Z'-O ₂ S- (CH ₂ ) _0. Substituted by _-1 , where Z'is as defined above and is a reactive dye with n = 1.

In the formula (I), n = 1, W = direct bond, and D is the general formula (IX).

[0085]

[Chemical 44]

[Wherein R ¹¹ is H, C ₁ -C ₄ -alkyl,
C ₁ -C ₄ -Alkoxy, Cl, Br, acylamino, especially C ₁ -C ₄ -alkylcarbonylamino or arylcarbonylamino, such as unsubstituted or substituted phenylcarbonylamino, C ₁ -C ₄ -alkylsulfonylamino, aminocarbonylamino. , C ₁ -C ₄ -alkylcarbonylamino and arylsulfonylamino, R ¹² is H,
C ₁ -C ₄ -alkyl, Cl, Br, C ₁ -C ₄ -alkoxy or COOH is shown, R ¹³ is H, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, SO ₃ H, Cl Or Br, and K is represented by the general formula (Xa)-(Xd).

[0087]

[Chemical formula 45]

Or

[0089]

[Chemical formula 46]

[0090]

[Chemical 47]

The divalent group of is represented by a bond represented by * is a group-
A reactive dye which is a group which is a bond to NR ¹ -B] is also a particularly preferred reactive dye.

B has the same meaning as in formula (VIa).

Particularly preferred groups Z and Z ', independently of one another, are -CH = CH ₂ or -C ₂ H ₄ -OSO ₃ H.

Suitable diazo components which are groups of the group D of the formula (IX) for the dyes of the formula (I) are, for example: aniline-
4-β-sulfatoethyl sulfone, aniline-4-β
-Thiosulfatoethyl sulfone, aniline-4-vinyl sulfone, aniline-3-β-sulfatoethyl sulfone, aniline-3-vinyl sulfone, 2-methoxyaniline-5-β-sulfatoethyl sulfone, 2-methoxyaniline -5-β-thiosulfatoethyl sulfone, 2-methoxyaniline-5-vinyl sulfone, 4-
Methoxyaniline-3-β-sulfatoethyl sulfone, 4-methoxyaniline-3-β-vinyl sulfone,
2,5-dimethoxyaniline-4-β-sulfatoethyl sulfone, 2,5-dimethoxyaniline-4-vinyl sulfone, 2-methoxy-5-methylaniline-4-β
-Sulfatoethyl sulfone, aniline-2-β-sulfatoethyl sulfone, 3- (3- or 4-aminobenzoyl) -aminophenyl-β-sulfatoethyl sulfone, 2-methoxy-5-methylaniline-4- Vinyl sulfone, 6-carboxyaniline-3-β-sulfatoethyl sulfone, 6-carboxyaniline-3-vinyl sulfone, 2-sulfoaniline-4-β-sulfatoethyl sulfone, 2-sulfoaniline-4-vinyl sulfone , 2,4-disulfoaniline-5-vinyl sulfone, 2-naphthylamine-8-β-sulfatoethyl sulfone, 2-naphthylamine-6-β-sulfatoethyl sulfone, 1-sulfo-2-naphthylamine-6- β
-Sulfatoethyl sulfone, 1-naphthylamine-4
-Β-sulfatoethyl sulfone, 1-sulfo-2-naphthylamine-5-β-sulfatoethyl sulfone, 6
-Sulfo-2-naphthylamine-8-β-sulfatoethyl sulfone, 2-amino-3-sulfonaphthalene-
6,8-bis- (β-sulfatoethyl sulfone), 1
-Naphthylamine-5-β-sulfatoethyl sulfone, 2-naphthylamine-5-β-sulfatoethyl sulfone, 2-naphthylamine-8-β-sulfatoethyl sulfone, 8-sulfo-2-naphthylamine-6-β
-Sulfatoethyl sulfone, 4-aminobenzyl-β
-Sulfatoethyl sulfone, 3-aminobenzyl-β
-Sulfatoethyl sulfone, 4-aminobenzyl vinyl sulfone, 3-aminobenzyl vinyl sulfone, 3-
Amino-4-sulfobenzyl-β-sulfatoethylsulfonyl, 4-amino-3-sulfobenzylvinylsulfone, 2 ′-(β-sulfatoethylsulfonyl) -3-
Sulfo-4-aminoazobenzene, 3 ′-(β-sulfatoethylsulfonyl) -3-sulfo-4-aminoazobenzene, 4′-methoxy-3 ′-(β-sulfatoethylsulfonyl) -3-sulfo-4 -Aminoazobenzene, 4'-vinylsulfonyl-2 ', 3-disulfo-4
-Aminoazobenzene, 2 '-(β-sulfatoethylsulfonyl) -6-methyl-3-sulfo-4-aminoazobenzene, 3'-(β-sulfatoethylsulfonyl) -6-methyl-3-sulfo-4 -Aminoazobenzene, 4 '-(β-sulfatoethylsulfonyl) -6-
Methyl-3-sulfo-4-aminoazobenzene, 4'-
(Β-sulfatoethylsulfonyl) -2,6-dimethyl-3-sulfo-4-aminoazobenzene, 3 ′-(β
-Sulfatoethylsulfonyl) -6-methoxy-3-
Sulfo-4-aminoazobenzene, 3 ', 4'-bis-
(Β-sulfatoethylsulfonyl) -6-methoxy-
3-Sulfo-4-aminoazobenzene, 4 ′-(β-sulfatoethylsulfonyl) -6-methoxy-3-sulfo-4-aminoazobenzene, 4 ′-(β-sulfatoethylsulfonyl) -2-methyl- 5-methoxy-3-
Sulfo-4-aminoazobenzene, 4 ′-(β-sulfatoethylsulfonyl) -2,5-dimethoxy-3-sulfo-4-aminoazobenzene, 3 ′-(β-sulfatoethylsulfonyl) -2,5- Dimethoxy-3-sulfo-4-aminoazobenzene, 2- (4'-amino-
3'-sulfophenylazo) -6- (β-sulfatoethylsulfonyl) -naphthalene, 2- (4'-amino-
6'-methyl-3'-sulfophenylazo) -1-sulfo-6- (β-sulfatoethylsulfonyl) -naphthalene, 2- (4'-amino-6'-methyl-3'-sulfophenylazo) -6- (β-Sulfatoethylsulfonyl) -naphthalene, 2- (4′-amino-3′-sulfophenylazo) -8-sulfo-6- (β-sulfatoethylsulfonyl) -naphthalene, and 2- (4'-amino-6'-methyl-3'-sulfophenylazo)-
It is 1,7-disulfo-5- (β-sulfatoethylsulfonyl) -naphthalene.

Suitable coupling components H- on which the radical K is based
Examples of K-NHR ¹ are:

[0096]

[Chemical 48]

[0097]

[Chemical 49]

Wherein * represents a coupling site, and m or p represents the meta or para position of the amino group with respect to the azo group.

Further preferred reactive dyes are R ¹ and R ² =
Independently of each other, H, CH ₃ or C ₂ H ₅ , j = 0 or 1,
X = F or Cl, and Z and Z ′ = independently CH
₂ -CH ₂ -OSO ₃ H or CH = CH ₂ in which formula (IX)
Are reactive dyes of the formula (I) having the dye group D of

Particularly preferred reactive dyes of formula (I) are R ¹
And a reactive dye having ^{R 2 = H, i = 0} , j = 0, r = 2, and Z 'and Z = dye radical D of the formula (IX) is a -CH ₂ CH ₂ OSO ₃ H.

Preferred dyes within the meaning of formula (I) having a dye group D of formula (IX) are the following formulas (43)-(52)
Is a dye of the formula

[0102]

[Chemical 50]

Groups X, i, R ² , j, r and Z
Is synonymous with the above:

[0104]

[Chemical 51]

[0105]

[Chemical 52]

[0106]

[Chemical 53]

In the formula, R ¹ = H, CH ₃ or C ₂ H ₅ , R ¹¹ =
H, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, C
1, Br, acylamino, especially C ₁ -C ₄ -alkylcarbonylamino or arylcarbonylamino, such as unsubstituted or substituted phenylcarbonylamino, C ₁ -C ₄ -alkylsulfonylamino, aminocarbonylamino, C ₁
-C ₄ - alkylcarbonylamino or _{^{arylsulfonylamino, R 12 = H, C 1}} -C 4 - alkyl, C ₁ -C ₄
-Alkoxy, Cl, Br or COOH, R ¹³ = H, C
₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, Cl, Br
Or SO ₃ H.

The fused ring indicated by a dash indicates that a naphthalene system is possible instead. The reactive dyes of the formula (I) are suitable for dyeing and printing most of a wide variety of substrates, for example silk, leather, wool and synthetic polyamide fibres, but in particular cellulose-containing materials having a fibrous structure, such as linen, cellulose, Suitable for dyeing and printing regenerated cellulose and especially cotton. These are the exhaust method
ion process) and conventional pad-dyeing processes, in the latter case the product is impregnated with an aqueous and optionally salt-containing dye solution, after alkali treatment or in the presence of alkali. In some cases, the dye is fixed under the action of heat.

The reactive dyes of the formula (I) are notable for high reactivity and excellent fixing capacity. Because of their di- or polyfunctionality, they are long liquors.
or)) gives a high fixation yield. They are characterized by tinting strength, which is relatively independent of dyeing temperature and can therefore be used in the exhaust process at low to medium dyeing temperatures. In the case of the pad-steam method, they require only short steaming times. They give dyeings with excellent color depth and excellent light and wet fastnesses.

[0110]

EXAMPLES Example 1 A) 0.15 mol formula

[0111]

[Chemical 54]

The compound of Example
(See 118) was stirred in 100 parts of water and 100 parts of ice and dissolved under neutral conditions. 0 ° C and pH 4-4.5
0.165 mol of 2,4,6-trifluoro-1,
3,5-triazine was added dropwise over 10 minutes. About 250
The following structure of the part:

[0113]

[Chemical 55]

An aqueous solution of the condensate containing was obtained.

B) 0.1 mol of 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid was suspended in 150 parts of water and dissolved under neutral conditions with a lithium hydroxide solution. 0.1 mol of the above condensation solution was added. 20 ° C
The pH was maintained at 4-4.5 with lithium carbonate at.
The reaction was complete after 8 hours. A solution was obtained.

C) 0.1 mol of 2-amino-1-naphthalenesulfonic acid is diazotized in a suitable manner and the diazotized product is coupled to the H-acid condensation product at pH 7.5-8.5. did. The dye was salted out by adding potassium chloride and isolated. Upon drying, about 35 g of salt-containing dye coupling agent was obtained, which had the structure

[0117]

[Chemical 56]

(Λ _max = 521 and 544 nm (H
₂ O)), which dyes cotton in red by the usual dyeing or printing processes in the case of reactive dyes.

Example 2 0.1 mol of 2-amino-1,5-naphthalenedisulfonic acid was suspended in 200 parts of water and 100 parts of ice at 0 ° C. 28 parts concentrated hydrochloric acid was added. A solution of 7 parts sodium nitrite in 70 parts water was added dropwise over 15 minutes. The mixture was then stirred for 30 minutes before the diazotization was complete. A pale yellow suspension resulted. Excess nitrite was destroyed with amidosulfonic acid.

This suspension is now added to 0.1 mol of Example 1
Weighed into the H-acid condensation product from B over 15-20 minutes. Coupling was performed at 20 ° C and pH 7-8. The dye was precipitated by the addition of ethanol and isolated. When dried, about 40 g of dye powder is obtained, which has a structure

[0121]

[Chemical 57]

(Λ _max = 518 and 539 nm (H
₂ O)), which dyes cotton in red by the usual dyeing or printing processes in the case of reactive dyes.

A red reactive dye is further obtained by condensation of the following components.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

[Table 3]

[0127]

[Table 4]

Example 19 0.1 mol formula

[0129]

[Chemical 58]

The monoazo compound having: was dissolved in about 500 parts of water under neutral conditions. 0.15 mol of the condensation solution prepared in Example 1 was added. The pH was kept at 7-8 with sodium carbonate solution at 20 ° C. After 2 hours, the reaction was almost complete. The dyestuff was salted out by addition of potassium chloride, isolated and dried. About 72 g of salt-containing dye powder is obtained, which has the formula

[0131]

[Chemical 59]

(Λ _max = 485 nm (H ₂ O)),
It dyes cotton orange by the usual dyeing or printing processes for reactive dyes.

Example 20 0.1 mol of 2-amino-5-methoxybenzenesulphonic acid was dissolved in 150 parts of water and 50 parts of ice under neutral conditions. 28 parts concentrated hydrochloric acid was added. A solution of 7 parts sodium nitrite in 70 parts water was added dropwise over 15 minutes. The mixture was then stirred for 30 minutes before the diazotization was complete.
Excess nitrite was destroyed with amidosulfonic acid.

0.12 mol of 7-amino-4-hydroxynaphthalene-2-sulfonic acid was suspended in 300 parts of water, and the pH was adjusted to 6 with a 10% lithium hydroxide solution.
It dissolved at -6.5. 0.18 mol of the condensation solution prepared in Example 1A was added. The pH was kept at 4-5 with sodium carbonate solution at 20 ° C. The condensation was complete after 2 hours. 900 parts of solution were obtained. The product was isolated by salting out with 180 parts of potassium chloride. About 220 parts of a gray paste was obtained. The paste was dissolved in 600 parts of water. The above diazotized mixture was added dropwise and NaHCO ₃
Was added simultaneously to maintain pH 6-6.5. Thereafter, the pH was adjusted to 7.5-8 using a sodium carbonate solution. The solution was stirred overnight.

The dye was salted out by adding sodium chloride and isolated. When dried, about 105 g of salt-containing dye powder is obtained, which has the structure

[0136]

[Chemical 60]

Which dyes cotton in deep red by the usual dyeing or printing processes in the case of reactive dyes.

Further reactive dyestuffs are obtained analogously to Examples 19 or 20 by condensation of trifluorotriazine and the following components:

[0139]

[Table 5]

[0140]

[Table 6]

[0141]

[Table 7]

[0142]

[Table 8]

Example 32 0.1 mole formula

[0144]

[Chemical formula 61]

The monoazo dye of (1) was dissolved in 500 parts of water under neutral conditions. 0.2 mol of the condensation solution prepared in Example 1A was added. The pH was kept at 7-8 for 8 hours with sodium carbonate solution at 20 ° C. About 1100 parts of dye solution were obtained. The dye was salted out with potassium chloride, isolated and dried. About 105 g of salt-containing dye powder is obtained, which has the structure

[0146]

[Chemical formula 62]

(Λ _max = 420 nm (H ₂ O)),
It dyes cotton yellow by the usual dyeing or printing processes for reactive dyes.

Further yellow reactive dyestuffs are obtained by condensation of the following components:

[0149]

[Table 9]

[0150]

[Table 10]

[0151]

[Table 11]

Example 45 0.1 mole formula

[0153]

[Chemical formula 63]

The monoazo dye of (1) was dissolved in 400 parts of water under neutral conditions. 0.15 mol of the condensation solution prepared in Example 1A was added. The pH of 7-8 was maintained for 8 hours with sodium carbonate solution at 20 ° C. About 1100 parts of dye solution were obtained. The dye was salted out with potassium chloride, isolated and dried. About 105 g of salt-containing dye powder is obtained, which has the structure

[0155]

[Chemical 64]

Which dyes cotton in yellow by the usual dyeing or printing processes in the case of reactive dyes.

The following aminophenylazopyrazolones are condensed with cyanuric fluoride and the compound of formula (V) shown to further give yellow dyes with similar properties.

[0158]

[Table 12]

[0159]

[Table 13]

Example 53 2-Aminonaphthalene to 3-aminoacetanilide-
45.3 g of coupling product of 6,8-disulfonic acid
Is dissolved in 600 ml of water with heating at 50 ° C. at pH 7. The formula prepared according to Example 1A after cooling to 20 ° C.

[0161]

[Chemical 65]

0.15 mol of the component (VIb) of (1) is added, and pH 7-7.5 is maintained for 8 hours using a sodium carbonate solution.

The solution obtained is evaporated in a vacuum at 35-40 ° C. after addition of 1.5 g of pH 6 phosphate buffer or spray-dried.

The formula obtained

[0165]

[Chemical formula 66]

The dye of (1) dyes cotton from long liquor to a golden color at an optimum dyeing temperature of 50 ° C. λ _max = 389n
m, underwater.

Condensation of the following p-aminoazo compounds with cyanuric fluoride or cyanuric chloride and a compound of formula (V) additionally gives dyes which give reddish-yellow dyeings.

[0168]

[Table 14]

[0169]

[Table 15]

[0170]

[Table 16]

[0171]

[Table 17]

Example 69 0.15 mole formula

[0173]

[Chemical formula 67]

The component of c is condensed with cyanuric fluoride according to example 17. The solution of the obtained condensation product,
Formula of 0.1 mol in 300 ml of water adjusted to pH 7 and cooled to 0-5 ° C.

[0175]

[Chemical 68]

The solution of the azo compound (1) was added to the mixture, while the pH of the mixture was adjusted to 6.5-7.5 using a dilute sodium carbonate solution.
Keep on. The temperature rises to 20-25 ° C. When the condensation is complete, the dye is isolated by salting out and suction filtration, pH 6.
Buffer to 5 and vacuum dry at 45 ° C. This is an expression

[0177]

[Chemical 69]

Corresponding to, cotton is dyed from long liquors in bluish red with a high fixing yield. A similar red dye is obtained by reaction of the following components.

[0179]

[Table 18]

[0180]

[Table 19]

[0181]

[Table 20]

Example 83 36.7 g of formula prepared by known route

[0183]

[Chemical 70]

The amino disazo compound of (1) is dissolved in 400 ml of water at pH 6.0. The value of 0.
15 mol of active ingredient (VIb) are added and the mixture is kept at 20 ° C.
And condense at pH 8 for about 8 hours.

The formula obtained

[0186]

[Chemical 71]

The dyestuff of item (1) was salted out with sodium chloride,
After suction filtration, buffering to pH 6 and vacuum drying at 45 ° C. In the case of reactive dyes, this dyes cotton in high yields in a known manner and brown.

Example 83a Instead of the aminodisazo compound of Example 83, the formula

[0189]

[Chemical 72]

Using the compound of formula

[0191]

[Chemical formula 73]

Dyes of ## STR15 ## are obtained which likewise dyes cotton in high yields in brown.

A brown reactive dye is further obtained by condensation of the following components.

[0194]

[Table 21]

Example 88 50.3 g of formula

[0196]

[Chemical 74]

The aminoazo compound (0.1 mol) of (1) is dissolved in 400 ml of water under neutral conditions. Add 0.15 mol of the condensation solution prepared in Example 1A. PH kept 8 hours 7-8 with Na ₂ CO ₂ solution. Then expression

[0198]

[Chemical 75]

The dyestuff from is isolated by salting out and suction filtration. After gentle drying, a powder which dyes cotton in a high yield in a deep red is obtained in the usual way.

A reactive dye based on an aminoazonaphthol compound is further obtained by condensation of the following components.

[0201]

[Table 22]

Example 93 35.2 g of known compound (0.05 mol)

[0203]

[Chemical 76]

Is dissolved in 350 ml of water and the pH of the solution is adjusted to 7.0. 0.06 mol of the condensation solution prepared in Example 1A is added to this solution. pH 7-8 and 20-25
The reaction is performed at 6 ° C for 6-7 hours.

After completion of the condensation reaction, buffer at pH 6 and
The dye is isolated directly by spray drying or by salting out, suction filtration and vacuum drying at 40 ° C. Dye is a formula

[0206]

[Chemical 77]

It dyes cotton in a very high yield in navy blue with the usual dyeing methods for reactive dyes.

General formulas listed in the table below

[0209]

[Chemical 78]

Condensation of the aminodisazo component of (3) with a trihalogenotriazine and a compound of formula (V) further gives a similar reactive dye which dyes cellulose fibers from navy blue to black.

[0211]

[Table 23]

[0212]

[Table 24]

Example 101 50 mmol formula

[0214]

[Chemical 79]

The copper complex compound of is 600 m at pH 6.5.
Dissolve in 1 l of water. 60 mmol of the formula prepared in Example 1A

[0216]

[Chemical 80]

The compound of Example 1 was added to the dye solution and the mixture was added to 20
Condensate at -25 ° C and pH 6.5-7. When the reaction is over, the formula

[0218]

[Chemical 81]

The dye of (1) is salted out, isolated, buffered to pH 6 and dried in a vacuum at 45 ° C.

The product dyes cellulose fibers navy blue with very high fixing yields by the customary dyeing processes for reactive dyes.

The known copper complex compounds listed in the table below are condensed with the trihalogenotriazine and the components of the formula (V) by the method described in Example 101 to give cotton in very high yields according to the usual dyeing methods. Further reactive dyestuffs to be dyed are obtained.

[0222]

[Table 25]

[0223]

[Table 26]

[0224]

[Table 27]

Further interesting dyes are, for example, from the ortho-disazo metal complex system: Example 113 Cotton dyes olive-colored.

[0226]

[Chemical formula 82]

Alternatively, for example Example 114 cotton is dyed green from an orthoaminoazo metal complex system.

[0228]

[Chemical 83]

The dye is

Example 115 3 mole formula

[0231]

[Chemical 84]

2-Phenylaminoethanol of 20-
1400 parts of sulfuric acid (concentration 100
%). The mixture was subsequently stirred for 2 hours. The melt thus obtained is put on ice at 0 ° C. and then 0-5 ° C.
It was stirred for 1 hour. The precipitated product was isolated. About 15
00 parts of ester are obtained as a pale beige paste, which has the following formula:

[0233]

[Chemical 85]

Is given. The entire paste was suspended in 2500 parts of water and the pH was adjusted to 7 using a 50% strength calcium hydroxide solution. Over 20 minutes at 60 ° C., 3 mol of mercaptoethanol and then 3 mol of potassium hydroxide (solution having a concentration of 50%) were added dropwise. The mixture was boiled under reflux for 8 hours. The oil obtained was separated. The aqueous phase was extracted by shaking with ether. After distilling the ether, the products were combined. 460 parts of the thio compound have the formula

[0235]

[Chemical 86]

Obtained as an oil having

¹ H-NMR (D ₆ -DMSO) δ = 2.58-2.75 ppm (6H, m) δ = 3.22 ppm (2H, t) δ = 4.80 ppm (1H, s) δ = 6 .50-6.61 ppm (3H, m) δ = 7.05ppm (2H, d) Example 116 460 parts thioether 1000 parts acetone and 1 part.
Picked up in 000 copies of water. 2.6 mol acetic anhydride was added dropwise over 1 hour. The temperature rose to about 45 ° C.
The mixture was subsequently stirred for 2 hours and 14 g of sodium tungstate was added. Then the concentration of 4.9 mol is 35%
H ₂ O ₂ was added dropwise over 1 hour. Temperature is 50-55 ℃
Rose to. Acetone was distilled and the remaining solution was cooled to 10 ° C. The product formed precipitated and was isolated. This gave 1020 parts of paste, which was given the following formula:

[0238]

[Chemical 87]

¹ H-NMR (D ₆ -DMSO) δ = 1.77 ppm (1H, s) δ = 3.21-3.38 ppm (4H, m) δ = 3.76 ppm (2H, q) δ = 4 .05 ppm (2H, t) δ = 5.10 ppm (1H, t) δ = 7.38-7.55 ppm (5H, m) Example 117 1010 parts of paste was suspended in 1500 parts of water to give 30
0 part of a 30% strength hydrochloric acid solution was added. The mixture was boiled under reflux for 3 hours. The solution was cooled to 10 ° C. and brought to pH 9 with sodium hydroxide solution. The oil obtained was separated. The aqueous phase was extracted by shaking with ethyl acetate. The formula obtained after distilling ethyl acetate

[0240]

[Chemical 88]

The oil fractions of were combined and dried. This gave 450 parts of sulfone as an oil.

¹ H-NMR (D ₆ -DMSO) δ = 3.23-3.55 ppm (6 H, m) δ = 3.85 ppm (2 H, t) δ = 5.30 ppm (1 H, s) δ = 5 0.78 ppm (1H, t) δ = 6.60 ppm (3H, d) δ = 7.10 ppm (2H, t) Example 118 450 parts of the above material at 1800 parts over 20 hours at 20-30 ° C. Was added dropwise to sulfuric acid. After 8 hours, the melt was poured onto ice and the mixture was subsequently stirred at 0-5 ° C for about 1 hour. A pale beige crystalline product was isolated. 910
Some pastes were obtained. The compound formed has the formula:

[0243]

[Chemical 89]

[0244]

Yields were all stages (Examples 115-118).
Is over 45-50%.

¹ H-NMR (D ₆ -DMSO) δ = 3.43 ppm (2H, t) δ = 3.50 ppm (2H, t) δ = 3.60 ppm (2H, t) δ = 4.11 ppm (2H , T) δ = 7.00 ppm (3H, d, d) δ = 7.30 ppm (2H, t) δ = 8.98 ppm (2H, s) Example 119 A) 0.15 mole formula

[0247]

[Chemical 90]

The compound of (1) was stirred in 100 parts of water and 100 parts of ice to obtain a neutral solution. 0.165 mol of 2,
4,6-trifluoro-1,3,5-triazine at 0 ° C
And pH 4-4.5 over 10 minutes. About 25
0 parts of the following structure:

[0249]

[Chemical Formula 91]

An aqueous condensate solution having was obtained.

B) 0.1 mol of 1-amino-8-hydroxy-3,6-naphthalenedisulfonic acid are suspended in 150 parts of water and the suspension is converted into a neutral solution with lithium hydroxide solution. did. 0.1 mol of the above condensation solution was added. Adjust the pH to 4-4.5 with lithium carbonate at 20 ° C.
Kept at. The reaction was complete after 8 hours. A solution was obtained. C) 0.1 mol of 1-sulfo-2-naphthylamine-6
-Β-Sulfatoethyl sulfone was diazotized by a suitable method and coupled with the H acid condensation product at pH 7.5-8.5. Salting out the dye by adding potassium chloride,
Isolated. After drying, about 35 g of salt-containing dye coupling agent was obtained, which had a structure of

[0252]

[Chemical Formula 92]

(Λ _max = 516 and 538 nm (H
₂ O)), which dyes cotton in red by the usual dyeing or printing processes in the case of reactive dyes.

Example 120 0.1 mol of 4- (β-sulfatoethylsulfonyl)
Aniline was suspended at 0 ° C. in 200 parts water and 100 parts ice. 28 parts concentrated hydrochloric acid was added. A solution of 7 parts sodium nitrite in 70 parts water was added dropwise over 15 minutes. After stirring for another 30 minutes, the diazotization was completed. A pale yellow suspension was obtained. Excess nitrite was destroyed with amidosulfonic acid.

This suspension was then metered into 0.1 mol of the H acid condensation product from Example 119B over 15-20 minutes. Coupling was performed at 20 ° C. and pH 7-8. The dye was precipitated by the addition of ethanol and isolated. After drying, about 40 g of dye powder is obtained, which has a structure

[0256]

[Chemical formula 93]

(Λ _max = 517 nm (H ₂ O)),
It dyes cotton red by the usual dyeing or printing processes for reactive dyes.

A red reactive dye is further obtained by condensation of the following components.

[0259]

[Table 28]

[0260]

[Table 29]

[0261]

[Table 30]

[0262]

[Table 31]

Example 138 0.1 mole formula

[0264]

[Chemical 94]

The monoazo compound of (1) was dissolved in about 500 parts of water under neutral conditions. 0.15 mol of the condensation solution prepared in Example 119 was added. The pH was kept at 7-8 with sodium carbonate at 20 ° C. After 2 hours, the reaction was almost complete. The dyestuff was salted out by addition of potassium chloride, isolated and dried. About 82 g of salt-containing dye powder is obtained, which has the structure

[0266]

[Chemical 95]

(Λ _max = 492 nm (H ₂ O)),
It dyes cotton orange by the usual dyeing or printing processes for reactive dyes.

Example 139 0.1 mol of 4-aminophenyl-β-sulfatoethyl sulfone was dissolved in 100 parts of water and 100 parts of ice under neutral conditions. 28 parts concentrated hydrochloric acid was added. A solution of 7 parts sodium nitrite in 70 parts water was added dropwise over 15 minutes. After stirring for another 30 minutes, the diazotization was completed. A pale yellow suspension was obtained. Excess nitrite was destroyed with amidosulfonic acid.

0.12 mol of 7-amino-4-hydroxy-2-naphthalenesulfonic acid was suspended in 300 parts of water, and the pH was adjusted to 10% using a lithium hydroxide solution.
It was dissolved at 6-6.5. 0.18 mol of Example 119
The condensation solution prepared in A was added. The pH was kept at 4-5 with sodium carbonate solution at 20 ° C. After 2 hours, the condensation is complete. 900 parts of solution were obtained. The product was salted out and isolated using 180 parts of potassium chloride. About 2
20 parts of a gray paste were obtained. 600 paste
Dissolved in some water. The pH was adjusted to 6-6.5 by adding the above diazotized mixture dropwise and simultaneously adding NaHCO _3.
Kept at. The pH was then adjusted to 7.5-8 with sodium carbonate solution. The solution was stirred overnight.

The dyestuff was salted out and isolated by addition of sodium chloride. After drying, about 105 g of salt-containing dye powder is obtained, which has the structure

[0271]

[Chemical 96]

It dyes cotton deep red by the usual dyeing or printing processes in the case of reactive dyes.

Similar to Examples 138 or 139, further reactive dyes are obtained by condensation of the following components.

[0274]

[Table 32]

[0275]

[Table 33]

[0276]

[Table 34]

Example 150 35.2 g of known compound (0.05 mol)

[0278]

[Chemical 97]

Is dissolved in 350 ml of water and the pH of the solution is adjusted to 7.0. 0.06 mol of the condensation solution prepared in Example 119A is added to this solution. pH 7-8 and 2
The reaction is carried out at 0-25 ° C for 6-7 hours.

After the condensation is complete, after buffering to pH 6, the dyestuff is isolated directly by spraying or by salting out, suction filtration and vacuum drying at 40 ° C. Dye is a formula

[0281]

[Chemical 98]

And dyeing cotton in a very high yield with navy blue by the usual dyeing methods for reactive dyes.

General formulas shown in the table below

[0284]

[Chemical 99]

Condensation of the aminodisazo component of (3) with a trihalogenotriazine and a compound of formula (V) additionally gives a similar reactive dye which dyes cellulose fibers from navy blue to black.

[0286]

[Table 35]

[0287]

[Table 36]

The main features and aspects of the present invention are as follows.

1. formula

[0290]

[Chemical 100]

[Wherein D represents a group of an organic dye of a monoazo, polyazo or metal complex azo type, W represents a direct bond or a bridging member, R ¹ represents H, OR, OSO
₃ H, SO ₃ H, COOR or C ₁ -C ₄ -alkyl optionally substituted by halogen, R being H,
CH ₃ or indicates C ^₂ H _5, R ₂ is H, C ₁ -C ₄ - _{alkyl, Cl, Br, C 1 -C} 4 - an alkoxy or COOH, i denotes 0 or 1, j is 0 1 or 2
r represents 2 or 3, preferably 2, X represents F, Cl or Br, and Z represents —CH═CH ₂ , —CH ₂ —CH ₂ —O.
_{SO 3 H, -CH 2 -CH 2} -Cl, -CH 2 -CH 2 -B
_{r, -CH 2 -CH 2 -S 2} O 3 H, -CH 2 -CH 2 -O-
_{CO-CH 3, -CH 2 -CH} 2 -OPO 3 H 2 or -CH ₂
--CH ₂ --OH, n represents 1 or 2], and a compound known from EP-A-70 806

[0292]

[Chemical 101]

[0293]

[Chemical 102]

Reactive dyes excluding.

2. In the reactive dye according to item 1, the following formula

[0296]

[Chemical 103]

[Wherein D is a group of an organic dye of a monoazo, polyazo or metal complex azo type and further contains no fiber-reactive group, and R ¹ and R ² are independently of each other H, CH ₃
Or C ₂ H ₅ , W is a direct bond or a bridging member or direct bond, i is 0 or 1, and j is 0 or 1.
X is F or Cl, Z is CH ₂ —CH ₂ —O
SO ₃ H or CH = CH ₂ , and n is 1 or 2.]
A reactive dye characterized by being compatible with.

3. In the reactive dye according to at least one of the first and second terms, the following formula

[0299]

[Chemical 104]

[Wherein D is a group of an organic dye of a monoazo, polyazo or metal complex azo type, does not further contain a fiber-reactive group, X is F, Z is CH ₂ —CH ₂ — OS
O ₃ H, R ¹ is H, and n is 1.].

4. In the reactive dye according to at least one of items 1-3, the following formula: [wherein B is a formula]

[0302]

[Chemical 105]

Containing groups of X, i, R ² , j, r and Z
Is synonymous with item 1.]:

[0304]

[Chemical formula 106]

Here, Sa = OCH ₃ or OC ₂ H ₅

[0306]

[Chemical formula 107]

[0307]

[Chemical 108]

[0308]

[Chemical 109]

Metal complexes of the dyes of formulas (12)-(42):

[0310]

[Chemical 110]

[0311]

[Chemical 111]

[0312]

[Chemical 112]

[0313]

[Chemical 113]

[0314]

[Chemical 114]

[0315]

[Chemical 115]

[0316]

[Chemical formula 116]

[0317]

[Chemical 117]

Embedded image wherein acyl = acetyl or optionally substituted benzoyl, R ¹⁴ ═H or optionally SO ₃
C ₁ -C substituted by H or NH _{2 2} - alkyl, R ¹ = H, CH ₃ or ^{_{C 2 H 5, R 3 =}} H or sulpho,
R ⁵ = H, CH ₃ , OCH ₃ or Cl, R ⁶ = H, C ₁ -C ₄
- alkyl, C ₁ -C ₄ - alkoxy, Cl, Br, CO
OH or SO ₃ H, R ⁷ = H, OH, NH ₂ , NHCOC
_{H 3, NHCOPh, Cl, C} 1 -C 4 - alkoxy or C ₁ -C ₄ - _{^{alkyl, R 8 = H, SO 3}} H, CH 2 SO
₃ H, Cl, C ₁ -C ₄ -alkylsulfonyl, CN, carbonamide especially CONH ₂ , R ⁹ = H, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, Cl, Br, acylamino, especially C _1- C ₄ -Alkylcarbonylamino or arylcarbonylamino, such as optionally substituted phenylcarbonylamino, C ₁ -C ₄ -alkylsulfonylamino, aminocarbonylamino, C ₁ -C ₄ -alkylsulfonylamino or arylsulfonylamino , And R ¹⁰ ═H, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, OH or SO ₃ H, and the condensed rings indicated by the dashes in the formula indicate that naphthalene systems are possible instead. Show]
A reactive dye characterized by being compatible with one of the following.

5. In reactive dye according to at least one of the Section 1-4, X = Cl, i = 0 , j = 0 or _{1, Z = -CH 2 -CH 2} -OSO 3 H, -CH = CH 2 or -CH ₂ -CH ₂ -Cl, and reactive dyes is R ² = H.

6. The reactive dye according to at least one of the items 1 to 5, wherein X = F, i = 0, j = 0,
Z = reactive dyes is a -CH ₂ -CH ₂ -OSO ₃ H or -CH = CH _2, and R ² = H.

7. In reactive dye according to one To Sukunakumo of the 1-6, wherein, Z = reactive dyes is a -CH ₂ -CH ₂ -SO ₃ H.

8. In reactive dye according to paragraph 1, group D is 1 or 2 groups _{Z'-O 2 S- (CH 2} ) 0-1 wherein, Z 'is -CH = CH _2, -CH ₂ - CH ₂ -OS
_{O 3 H, -CH 2 -CH 2} -Cl, -CH 2 -CH 2 -B
_{r, -CH 2 -CH 2 -S 2} O 3 H, -CH 2 -CH 2 -O-
_{CO-CH 3, -CH 2 -CH} 2 -OPO 3 H 2 or -CH ₂
-CH ₂ OH].

9. In the reactive dye according to item 8, n
= 1, W = direct bond, and D is general formula (IX)

[0324]

[Chemical 118]

[Wherein R ¹¹ is H, C ₁ -C ₄ -alkyl,
C ₁ -C ₄ -alkoxy, Cl, Br or acylamino, R ¹² is H, C ₁ -C ₄ -alkyl, Cl, Br, C
_1- C ₄ -alkoxy or COOH, R ¹³ is H, C
₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, SO ₃ H,
Cl or Br, and K is represented by the general formula (Xa)-(Xd).

[0326]

[Chemical formula 119]

[0327]

[Chemical 120]

A divalent group of, and the bond marked with * is a group-
Is a bond to NR ¹ -B, and B has the same meaning as in item 4.]
A reactive dye characterized by being a group of.

10. In the reactive dye according to item 9,
R ¹ and R ² are each independently H, CH ₃ or C ₂ H ₅ , j is 0 or 1, X is F or Cl, and Z and Z ′ = independently CH ₂ — CH ₂ —OSO ₃ H or CH═CH ₂ is a reactive dye.

11. In the reactive dye according to item 1,
D represents a dye group of formula (IX), R ¹ and R ² = H, i =
0, j = 0, r = 2, and Z ′ and Z = —CH ₂ CH ₂ O
A reactive dye which is SO ₃ H.

12. In the reactive dye according to item 9,
The following formula, [where B is the formula:

[0332]

[Chemical 121]

Including a group of]:

[0334]

[Chemical formula 122]

[0335]

[Chemical 123]

[0336]

[Chemical formula 124]

[Wherein R ¹ = H, CH ₃ or C ₂ H ₅ , R ¹¹
= H, C ₁ -C ₄ - alkyl, C ₁ -C ₄ - alkoxy, acylamino, Cl or ^{Br, R 12 = H, C} 1 -C 4 - alkyl, C ₁ -C ₄ - alkoxy, Cl, Br or COO
H, R ¹³ = H, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, Cl, Br or SO ₃ H, and the fused ring indicated by a dash may be naphthalene-based instead. The present invention is a reactive dye characterized in that

13. formula

[0339]

[Chemical 125]

[Wherein D is a group of an organic dye of a monoazo, polyazo or metal complex azo type, W is a direct bond or a bridging member, R ¹ is H, or OR, OSO
₃ H, SO ₃ H, COOR or C ₁ -C ₄ -alkyl optionally substituted by halogen, R being H,
CH ₃ or C ₂ H ₅ , R ² is H, C ₁ -C ₄ -alkyl, Cl, Br, C ₁ -C ₄ -alkoxy or COOH, i is 0 or 1 and j is 0. 1 or 2,
r is 2 or 3, in particular 2, X is F, Cl or Br, Z is _{-CH = CH 2, -CH 2 -CH} 2 -OSO
_{3 H, -CH 2 -CH 2 -Cl} , -CH 2 -CH 2 -Br,
_{-CH 2 -CH 2 -S 2 O 3} H, -CH 2 -CH 2 -O-CO
_{-CH 3, -CH 2 -CH 2 -OPO} 3 H 2 or -CH ₂ -C
H ₂ —OH and n is 1 or 2] in the method for producing a reactive dye,

[0341]

[Chemical formula 126]

Dyes and formulas of nmole

[0343]

[Chemical 127]

By condensation of the trihalogenotriazine of formula

[0345]

[Chemical 128]

The compound of formula (IV) is obtained by

[0347]

[Chemical formula 129]

A further condensation with a component of formula b) or b) the first condensation product by condensation of the trihalogenotriazine of formula (III) with the component of formula (V) in reverse order.

[0349]

[Chemical 130]

And further condensing n moles of a compound of formula (VI) with a dye of formula (II), or c) condensation of a suitable starting material with a trihalogenotriazine (III) and a component of formula (V). , Or suitable raw material and formula (V
A process characterized by following the condensation of the first condensation product of I) and the subsequent production by dye synthesis.

14. A method for dyeing and printing a substrate using a reactive dye, which comprises using the reactive dye according to item 1.

15. General formula

[0353]

[Chemical 131]

[Wherein R ² , Z, j, i, and r have the same meanings as those in the first item], and their reaction products with a salt and a protecting group are represented by the formula:

[0355]

[Chemical 132]

Compounds other than the compounds of.

16. formula

[0358]

[Chemical 133]

In the production method of [wherein R ² , Z, j, i and r have the same meanings as in the first term],

[0360]

[Chemical 134]

By sulfation of the compound of and subsequent reaction with mercaptoethanol

[0362]

[Chemical 135]

By the protection of the NH group, optionally with a protecting group, and oxidation.

[0364]

[Chemical 136]

And optionally cleaving the protecting group

[0366]

[Chemical 137]

And optionally converting the group SO ₂ C ₂ H ₄ —OH to a vinylsulfonyl group or the —CH ₂ —CH ₂ —OH group to the other removable groups mentioned as Z. A method characterized by conversion.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ekhard Botsk Federal Republic of Germany Day 5067 Kürten-Bechen Kernassyutraße 360 (72) Inventor Bolframm Redeiich Federal Republic of Germany Day 5060 Bergiscyu-Gratbacher im Alten Felt 2 (72) Inventor Thomas Aitzenhefuer Day 5000 Cologne, Germany 60 Cologne 60, Johannes-Miular-Schütlerse 3 (72) Inventor Wolfgang Harms Day 5068, Germany Odentar Le Ozenauer Schyutraße 45 (72) Inventor Karl-Joseph Hert Germany Day 5068 Odenthal-Holts Amgarten Felt 66

Claims (4)

[Claims] 1. The formula: [Wherein D represents a group of a monoazo, polyazo or metal complex azo type organic dye, W represents a direct bond or a cross-linking member, R ¹ is H, OR, OSO ₃ H, SO ₃ H,
COOR or C ₁ -C ₄ -alkyl optionally substituted by halogen, R being H, CH ₃ or C ₂ H
₅ , R ² is H, C ₁ -C ₄ -alkyl, Cl, Br,
C ₁ -C ₄ -alkoxy or COOH, i represents 0 or 1, j represents 0, 1 or 2, r represents 2 or 3, preferably 2, X represents F, Cl or Br. shown, Z is _{-CH = CH 2, -CH 2 -CH} 2 -OSO 3 H, -CH 2
_{-CH 2 -Cl, -CH 2 -CH 2} -Br, -CH 2 -CH
_{2 -S 2 O 3 H, -CH} 2 -CH 2 -O-CO-CH 3, -C
H ₂ —CH ₂ —OPO ₃ H ₂ or —CH ₂ —CH ₂ —OH, and n represents 1 or 2] and EP-A-70.
Compounds known from 806 [Chemical 3] Except for reactive dyes. 2. The formula: [Wherein D is a group of an organic dye of a monoazo, polyazo or metal complex azo type, W is a direct bond or a bridge member, R ¹ is H, OR, OSO ₃ H, SO ₃ H,
COOR or C ₁ -C ₄ -alkyl optionally substituted by halogen, R being H, CH ₃ or C ₂ H
₅ and R ² is H, C ₁ -C ₄ -alkyl, Cl, Br,
C ₁ -C ₄ -alkoxy or COOH, i is 0 or 1, j is 0, 1 or 2, r is 2 or 3, especially 2, X is F, Cl or Br. , Z is -CH
_{= CH 2, -CH 2 -CH 2} -OSO 3 H, -CH 2 -CH 2
_{-Cl, -CH 2 -CH 2 -Br,} -CH 2 -CH 2 -S 2
_{O 3 H, -CH 2 -CH 2} -O-CO-CH 3, -CH 2 -
A CH ₂ -OPO ₃ H ₂ or -CH ₂ -CH ₂ -OH,
n is 1 or 2], a) Dyes and nmoles of the formula By condensation of a trihalogenotriazine of the formula To obtain a compound of formula (IV) in nmole of the formula: Or b) in the reverse order by condensing the trihalogenotriazine of formula (III) with the component of formula (V) in the reverse order to give a first condensation product And further condensing n moles of the compound of formula (VI) with the dye of formula (II), or c) condensation of a suitable starting material with the trihalogenotriazine (III) and components of formula (V), or Raw material and formula (V
A process characterized by following the condensation of the first condensation product of I) and the subsequent production by dye synthesis. 3. A method for dyeing and printing a substrate using a reactive dye, wherein the reactive dye according to claim 1 is used. 4. A general formula: [Wherein R ² , Z, j, i and r have the same meanings as defined in claim 1], and include a salt thereof and a reaction product with a protecting group. Compounds other than